Process for the treatment of a liquid mass

ABSTRACT

A process for treatment of a liquid mass is described, wherein a liquid mass of a material is separated from a gas-permeable wall for shaping, positioning or moulding the same by means of a gaseous film formed by a gas permeating through a wall of the container.

BACKGROUND OF THE INVENTION

The present invention relates to a process for the treatment of a liquidmass enabling the latter to be raised, positioned and moulded withoutcontact with the walls of a container and in particular permitting theshaping of materials by solidification.

Processes involving shaping by moulding lead to considerable problemswhen the liquids are corrosive, as is the case with high temperaturemetal alloys. The main problems caused are those of physical andphysicochemical compatibilities between the material forming thecontainer and the liquid. Reactions can take place between the twomaterials, which is prejudicial to the purity of the product obtained,whilst there can be incompatible dimensional variations duringsolidification and as a function of the relative values of the thermalexpansion coefficients.

This has led to the use of new methods serving to eliminate thecontainers through the action of electromagnetic, electrostatic,acoustic and even optical lifting forces. However, these methods aredifficult to use and can only be applied to small masses under theearth's gravity. Moreover, they do not permit the shaping of liquidmasses.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to a process obviating the aforementioneddisadvantages by permitting the lifting and handling of possibly largeliquid masses without contact with the walls of a container.

The present invention therefore specifically relates to a process forthe treatment of a liquid mass in an apparatus having at least one wall,wherein the liquid mass is raised, positioned or moulded without anycontact with the wall as a result of a gaseous film flowing through thesaid wall, the gas being chemically inert with respect to the liquidmass the material from which the wall is made.

According to another feature of the present process, the wall is porousor is perforated by narrow ducts in order to permit the passage of thegas used for raising and handling purposes. When the wall is porous, itcan be made from a fritted material.

Thus, through preventing any mechanical contact between the liquid andits container, there are no interactions between the liquid and thematerial from which the walls are made and as a result large liquidmasses can be kept in a container. Obviously the gas used for thehandling operations must be chemically inert with respect to the liquidand in numerous applications a neutral gas such as helium can besuitable.

Advantageously the container walls are porous and the gaseous film isproduced by a forced outflow thereof through the container walls fromthe outside towards the surface of the liquid. In this way a normaluniform dynamic pressure is established at all points of the surface andthis balances the pressure forces exerted by the liquid. The stabilityof the gaseous film, which is an essential condition for maintaininginsulation between the liquid and the wall, is obtained by checking theoutflow of the gaseous flux in order to prevent oscillations of theliquid surfaces.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention is described in greater detail hereinafter relative tonon-limitative embodiments and the attached drawings, wherein show:

FIG. 1 a diagrammatic sectional view of a liquid drop supported by agaseous film above a horizontal porous wall.

FIG. 2 a similar view to that of FIG. 1 illustrating the displacement ofthe liquid drops maintained by the gaseous film above a horizontalporous wall.

FIG. 3 a diagrammatic sectional view showing a liquid mass contained ina container using the process of the invention.

FIG. 4 a diagrammatic sectional view illustrating a vertical zonemelting process, the melted part of a solid member being containedwithin a sleeve without contact with the walls thereof.

FIG. 5 a vertical drawing or pulling process.

FIGS. 6a and 6b a process for maintaining and shaping a solid materialby melting a horizontal area in which a sleeve moves along the solidmember, the melted area being separated from the sleeve walls by agaseous film.

FIG. 6c a horizontal area melting apparatus.

FIG. 7 a diagrammatic view of an elongated liquid mass placed underspatial microgravity and maintained with the aid of porous wallsdiffusing a gaseous film.

FIG. 8 a diagrammatic sectional view of a continuous casting process inwhich part of the liquid mass in the container flows in a sleeve, whilstbeing separated from its walls by a gaseous film.

FIG. 9 a diagrammatic sectional view of a process for shaping the solidmember by vertical solidification using the process according to theinvention.

FIG. 10 a process for shaping a photovoltaic silicon plate by verticalpulling using the lifting process according to the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

FIG. 1 shows how a liquid silicon drop 2 can be supported above a wall 4by means of a gaseous film without any contact between drop 2 and thewall 4. Wall 4 is porous and constitutes the diffusing wall of a chamber6 permitting the pressurization and heating of the gas used. A liquiddrop can either be placed in direct contact with the wall and raised byforcing a gaseous mass through the wall or a solid mass can be used,which is raised by a gaseous film and then melted. In the particularcase shown in FIG. 1, a parallelepiped of approximately 10 g of solidsilicon is placed in the centre of a graphite plate 4 with a 32% openporosity, the plate thickness being approximately 3 mm. The solidsilicon block is firstly raised by diffusing the helium through the wall4. The assembly is placed in a resistance oven, which induces noelectromagnetic force on the silicon mass, heating is started up and isincreased until the silicon melts. The latter is collected in the formof drops, essentially under the action of the high surface tension ofthe liquid silicon. To maintain drop 2 at the same point on the outersurface of plate 4, the latter is given a slightly concave shape. Thus,as the weight of the drop is balanced by the pressure of the gaseousfilm if no restoring force maintains it, it acquires a considerablemobility under the effect of minimal, uncontrolled forces. Thus, aslightly concave wall shape is used to prevent an accidentaldisplacement of the drop.

However, in certain cases it may be necessary to displace liquid dropsheld above a horizontal wall by a gaseous film.

FIG. 2 illustrates a process permitting such an operation. It ispossible to see two drops 8, 10 held above a porous wall 12 by a gaseousfilm according to the process of the invention. The raising gas arrivesthrough an opening 14 in a chamber 16 and diffuses through wall 12. Forthe displacement of drops 8 and 10, local overpressures orunderpressures are produced and for this purpose slide valves 18 movingwithin chamber 16 are used. Each of the moving slide valves 18 beingcontrolled by rods 19 has a thin porous plate 20, of the same type aswall 12 and which locally increases the pressure drop of the gases, thusproducing pressure reductions on the wall in which the drops 8 and 10are stabilized. The displacement of the slide valves 18 by means of rods19 brings about the displacement of the underpressure areas andconsequently of the drops.

The processes described hereinbefore with reference to FIGS. 1 and 2 areonly applicable to small drops or liquid masses. In the case of largermasses, it is necessary to use containers in which the liquid mass isseparated from the walls by a gaseous film.

FIG. 3 illustrates a process for maintaining a liquid mass 22 within acontainer 23 without any part of the mass being in contact with thewalls or bottom of the container. The walls 24 of the latter are porousin order to permit the passage of the gas used for raising andpositioning purposes. The base 25 of container 23 is also formed by aporous wall through which is supplied the gas used for raising purposes.It is pointed out that in this case the gas films between the bottom ofthe container and the liquid mass on the one hand and between thecontainer walls and the liquid mass on the other do not fulfil the samefunction. The pressure of the gaseous film between the bottom 25 and theliquid 22 only serves to compensate the weight of the latter, whereasthe gaseous film between the liquid and container walls 24 is used forcompensating the variable hydrostatic pressure of the liquid column.Moreover, bottom 25 of container 23 is not in contact with walls 24.Thus, an opening 26 is made in the lower part of the container to permitthe flow of diffused gas through the porous walls.

The process according to the invention has numerous, variedapplications, particularly for the shaping of materials from a liquidmass. It is particularly useful in zone melting processes. Existing zonemelting processes have disadvantages, particularly when the startingmember is in the vertical position. This is due to the lack of stabilityof the liquefied zone, which may collapse under the action of its ownweight, when the height of the liquid part is excessive. The processaccording to the invention obviates these disadvantages by making itpossible to maintain in place materials undergoing a zone meltingoperation, even when the liquefied zone has large dimensions (height anddiameter). For this purpose the melted zone is kept within a sleevehaving porous walls by means of a gaseous film and no point of themelted mass is in contact with the sleeve walls. Obviously the sleevecross-section can be of a random type making it possible to obtainvaried profiles.

FIG. 4 illustrates a process for maintaining in a given form a liquidportion of a metal member, e.g. a monocrystalline metal member 27 placedin a vertical zone melting apparatus. Member 27 is placed within aheating sleeve 28 having porous walls 29 in order to permit the passageof a pressurized gas. Sleeve 28 is vertically displaced. The liquefiedpart 32 of member 27 is maintained without direct contact with thesleeve walls 29 by the gas diffused through the same. During thevertical displacement of sleeve 28, there is a simultaneous displacementof the melted zone 32. Obviously the process is also applicable in thecase when the member moves within the sleeve, whilst the latter remainsfixed.

FIG. 5 illustrates a vertical pulling or drawing process, which is alsocalled the CZOCHRALSKI process. In conventional manner, this consists ofbringing a very fine tube into contact with the free surface of a meltedmaterial. By capillarity the liquid rises along the tube and solidifies,so as to form a nucleus. The tube is then raised very slowly and theliquid adhering to the nucleus solidifies during this displacement. FIG.5 illustrates such a process, in which the liquid mass is kept out ofcontact with the walls of the container by the process of the invention.It can be seen that the liquid part 36 of material 35 is maintained by adiffusing, heating sleeve 38, the finished, drawn part is shown at 34.

The case of horizontal zone melting with modification of thecross-section is illustrated by FIGS. 6a and 6b showing a solid member42 held horizontally by its two ends and a sleeve 43 permitting areduction of the cross-section surrounding member 42 and whose walls 44are porous. This sleeve can move along member 42 in the directionindicated by arrow F. Heating means 45 make it possible to liquefy thatpart of member 42 located within it, the liquid mass 46 being held andshaped within the sleeve as a result of a pressurized gaseous filmsupplied through the effusing walls 44. In the special case describedhere, FIG. 6a is a side view of the apparatus used in which sleeve 43 isshaped like a cradle, whilst FIG. 6b is a plan view of the sameapparatus. It is a question here of reducing the width of member 42 andfor this purpose sleeve 43 is given a random shape in order that theliquefied part 46 can bring about the connection between the alreadyfinished part 42a and the part of member 42 which is to be narrowed orcontracted, i.e. 42b. In the present embodiment member 42 is lengthenedand then its width is reduced without modifying its height. For thispurpose only the first end 48 of member 42 is fixed, whilst the otherend 47 can move progressively within a support 50. FIGS. 6c shows anapparatus for carrying out horizontal zone melting without any variationof the cross-section, in which sleeve 43' has a U-shaped cross-sectionand supports the liquid zone 46' by means of gas diffused through theporous walls 44'. Obviously sleeve 43' can be broken down into twovertical walls and an independent horizontal base. Heating means 45'melt member 42'. It is clear that in all cases there is no contactbetween the liquefied part of member 42 and the walls of sleeve 43.

The process of the invention can also be used for the production ofmaterials in spatial microgravity, a field in which the liquids areindeed raised, but their positioning and shaping are not assured. FIG. 7illustrates such an application in which a liquid mass 51 is kept in anelongated form without contact in microgravity. The positioning of mass51 is ensured by guide rails 52 having effusing porous walls 53 throughwhich is introduced a gas. As no weight or hydrostatic pressure isexerted, the necessary gaseous flows can be relatively small.

FIG. 8 illustrates a continuous casting process using the gaseous filmraising or lifting process according to the invention. A liquid mass 54is contained within a container 55, whose base has an opening 56 for thedischarge of liquid and its solidification by continuous casting. Theliquid flowing through opening 56 passes through a sleeve 57, whosewalls 58 are porous in order to permit the passage of a pressurized gas.In the upper part of sleeve 57 there is another horizontal porous wall59 facing the outer wall of the bottom of container 55 and which is at avery limited distance from the latter. The gaseous film difused in thisway between wall 59 and the container bottom prevents the start ofwetting by the liquid flowing through opening 56 of the inner face ofthe sleeve. A level detector 60 connected to a supply 61 controls theinflow of liquid as a function of the drop of level thereof withincontainer 55. An appropriate setting of the temperature of the gasdiffusing through walls 58 makes it possible to position thesolid-liquid interface at an appropriate point within sleeve 57. In thecase of continuous casting illustrated in FIG. 8, it can be seen thatthe liquid mass 54 is in contact with the walls of container 55, but isnot in contact with the walls of the shaping member or sleeve 57. Thisis admissible when there is substantially no interaction between theliquid and the walls of container 55 or when it is not wished to producevery high purity material. However, if it is desired to produce amaterial with a very high purity level, it is possible to use acontainer 55, whose bottom and walls are porous like those of sleeve 57,in order to permit the passage of a pressurized gas. Thus, the liquidmass is separated from all the walls of the production apparatus by apressurized gas film.

The process of the invention can also be used in the shaping of materialby vertical solidification from the top. This consists of carrying outthe forced immersion of a shaping member having an opening provided withan effusing sleeve so as to bring about the rise of the liquid in thesleeve.

FIG. 9 illustrates such a process in which a solid member 63 is producedfrom a liquid mass 64 in a container 65. The latter is placed in an oven62 in order to keep mass 64 liquid. The maintaining in position of thatpart of the liquid mass adhering to the solidified portion 63 is broughtabout by the process of the invention. For this purpose a device 66called a "shape member" is placed above the free surface of liquid 64.This device has external dimensions which are slightly smaller thanthose of container 65 and has at its centre an opening defining apassage 67 for producing the solidified portion 63. The walls of theshape member 66 facing the inner wall of container 65, facing the freesurface of liquid 64 and in sleeve 67 are porous in order to permit thepassage of a gas introduced through opening 70. The gas diffusingthrough the porous walls of member 66, after partial immersion of thelatter in the bath, make it possible to maintain part of the liquid masswithin the sleeve 67. The shaped liquid solidifies in sleeve 67. The gasdiffusing through the walls facing the free surface of liquid 64 is usedfor insulation purposes and the gaseous film interposed between theouter walls of member 66 and the inner wall of container 65 prevents theliquid from rising along the latter. As the solid portion 63 is shaped,the level of liquid 64 in container 65 drops. As the shape member 66 hasa fixed position, a device is provided for raising the container duringproduction.

Finally, another interesting application of the process according to theinvention is the shaping, by vertical drawing, of photovoltaic siliconplates. FIG. 10 shows an apparatus for applying such a process. It ispossible to see a molten silicon mass 71 in a vitreous carbon crucible72, placed on a height-regulatable support (not shown). Above the freesurface of the liquid 71 is arranged a shape member 73 having in itscentre a vertical slot defining a sleeve 74 of width 1 mm, height 10 mmand length 50 mm, whose walls 75 are porous. The assembly is placed inan oven 79. Wall 76 of member 73 facing the free surface of liquid 71 isalso porous. Gas is supplied into the interior of member 73 by an inletpipe 77. Initially the lower wall 76 of member 73 is brought into thevicinity of the free surface of liquid 71. The gas is then introducedand the temperature within the slot stabilized at a few degrees belowthe melting point of the silicon. A 0.5 mm thick, flat nucleus is thenintroduced into slot 74 until it is in contact with the surface of theliquid. A solid-liquid interface is then formed and its position is thenfixed within the slot by an appropriate setting of the heating means ofoven 79. Drawing or pulling can then commence at the desired speed. Theliquid level drops as plate 78 is formed. As the shape member is fixedwith respect to oven 79, bath level variations are compensated by acontinuous rise of crucible 72. It is also pointed out that in theapplications illustrated in FIGS. 9 and 10, the liquid is in contactwith the walls 65 and 72 of the container containing it. On desiring toproduce a very high purity material, it is possible to use porous wallsand the comments made hereinbefore in connection with continuous castingalso apply here.

The process of the invention has numerous advantages, because it permitsthe shaping of solid materials from a liquid mass without any contactbetween the latter and the container walls. This prevents any possibleinteraction and makes it possible to obtain a high purity end product.The process is applicable to various shaping methods, particularly zonemelting, continuous casting, solidification by vertical drawing and theproduction of high purity glass. It can also be used in maintaining andpositioning liquid masses in microgravity. It also makes it possible todisplace liquid masses above a horizontal wall without any contact withthe latter.

Finally it is obvious that the invention is not limited to theembodiments described and numerous variants are possible thereto withoutpassing beyond the scope of the invention, particularly with regards tothe choice of the lifting gas and the materials used for forming theporous walls for the diffusion thereof.

What is claimed is:
 1. A process for the treatment of a liquid masscomprising the steps of providing an apparatus having at least onegas-permeable wall made from a porous fritted material or perforated bynarrow ducts, said wall being level and of substantially planar shape,causing a pressurized gas to flow through said wall, disposing saidliquid mass in the vicinity of said wall whereby a pressurized gaseousfilm supporting said mass is formed separating said liquid mass fromsaid wall, and positioning said mass without any contact thereof withsaid wall, by locally varying the pressure of said gaseous film bymoving a member on the side of said wall opposite to that where saidliquid mass is located, said gas being chemically inert with respect tosaid liquid mass and the material from which said wall is made.
 2. Aprocess for the treatment of a liquid mass comprising the steps ofproviding a container having gas-permeable bottom and side walls madefrom a porous fritted material or perforated by narrow ducts, causing apressurized gas to flow through said walls, disposing said liquid massin the vicinity of said walls, whereby a pressurized gaseous filmsupporting said mass is formed separating said liquid mass from saidwalls and raising, positioning or moulding said mass without any contactthereof with said walls, said gas being chemically inert with respect tosaid liquid mass and the material from which said wall is made, and saidmass being kept away from the bottom and side walls of the container inorder to permit the passage of the gas used for forming said pressurizedgaseous film.
 3. A process for shaping a material by zone meltingstarting from a solid member comprising the steps of providing agas-permeable sleeve open at each end, said sleeve being made from agas-permeable porous fritted material or perforated by narrow ducts,causing a pressurized gas to flow through said sleeve, disposing saidmember in said sleeve, whereby a pressurized gaseous film supportingsaid member is formed separating said member from said sleeve,progressively displacing said sleeve with respect to said member whileheating said sleeve to melt that part of said member adjacent saidsleeve, the liquified part of said member being kept remote from thewalls of said sleeve by said pressurized gas, said gas being chemicallyinert with respect to said member and the material from which saidsleeve is made.
 4. A process for production of a solid member byvertical drawing from a liquid mass comprising the steps of providing agas-permeable sleeve open at each end, said sleeve being made from a gaspermeable porous fritted material or perforated by narrow ducts, causinga pressurized gas to flow through said sleeve, disposing said liquidmass in said sleeve while heating said sleeve whereby a pressurizedgaseous film supporting said mass is formed separating said liquid massfrom said sleeve, and vertically drawing said mass without any contactthereof with said sleeve, said gas being chemically inert with respectto said liquid mass and the material from which said sleeve is made. 5.A process according to claim 4 for production of a solid member fromabove, wherein said liquid mass is introduced beneath said sleeve, andlifting a solidified member from above said sleeve.
 6. A processaccording to claim 5 for shaping of a solid member by vertical upwarddrawing from a liquid mass contained in a container wherein the part ofthe liquid mass adhering to the solidified portion of the member is keptvertical by means of a device placed about the free surface of theliquid and having at least one opening defining a sleeve for the passageof the solidified material, the liquid-solid interface being locatedwithin the said sleeve, whose walls are porous, in order to permit thepassage of the gas used for the lifting of the vertical part of theliquid mass, the device also having at least one porous wall facing thefree surface of the liquid in order to keep the latter horizonatal inthe vicinity of the sleeve with the aid of a pressurized gas traversingthe said wall.
 7. A process for the treatment of a liquid masscomprising the steps of providing an apparatus having at least onegas-permeable wall, made from a porous fritted material or perforated bynarrow ducts, causing a pressurized gas to flow through said wall,disposing said liquid mass in the vicinity of said wall whereby apressurized gaseous film supporting said mass is formed separating saidliquid mass from said wall, and suspending said liquid mass byapplication of a spatial micro-gravity force field, to elevate said massbetween opposed porous walls on the surfaces of which said gaseous filmis formed, said gas being chemically inert with respect to said liquidmass and the material from which said wall is made.
 8. A processaccording to claim 7, which includes the step of providing apparatuscomprising at least three members serving as guides for said mass, eachof said members having a porous wall facing said mass, and passingpressurized gas therethrough to form said gaseous film.